WO2001019834A1 - Preparation of benzenediboronic acid via a disilylated aryl-intermediate - Google Patents

Preparation of benzenediboronic acid via a disilylated aryl-intermediate Download PDF

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Publication number
WO2001019834A1
WO2001019834A1 PCT/GB2000/003554 GB0003554W WO0119834A1 WO 2001019834 A1 WO2001019834 A1 WO 2001019834A1 GB 0003554 W GB0003554 W GB 0003554W WO 0119834 A1 WO0119834 A1 WO 0119834A1
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process according
radical
boronic acid
substituted
boronic
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PCT/GB2000/003554
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French (fr)
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Richard O'dell
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Cambridge Display Technology Limited
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Priority claimed from GBGB9921988.3A external-priority patent/GB9921988D0/en
Application filed by Cambridge Display Technology Limited filed Critical Cambridge Display Technology Limited
Priority to AU74324/00A priority Critical patent/AU7432400A/en
Publication of WO2001019834A1 publication Critical patent/WO2001019834A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3

Definitions

  • the present invention relates to a process for synthesizing monomers for preparing polymers such as a conjugated polymer for use in an optical device such as an electroluminescent device.
  • Organic electroluminescent devices which employ an organic material for light emission.
  • O90/13148 describes such a device comprising a semiconductor layer comprising a polymer film which comprises at least one conjugated polymer situated between electrodes.
  • the polymer film in this case comprises a poly (para-phenylene vinylene) (PPV) film which is capable of light emission when electrons and holes are injected therein.
  • PPV poly (para-phenylene vinylene)
  • Other polymer layers capable of transporting holes or transporting electrons to the emissive layer may be incorporated into such devices.
  • the bandgap of PPV and other poly(arylene vinylene) polymers may be tuned to modulate the wavelength, quantum efficiency and/or refractive index thereof, as described in EP-A-0544795.
  • poly(arylene vinylene) s for use in optical devices has been conveniently carried out by a precursor route where thermal elimination of leaving groups gives rise to a conjugated polymer, or by other routes such as a dehydrohalogenation reaction.
  • poly(arylene vinylene) s are not the only class of polymers which are suitable for use in optical devices.
  • Other aryl- containing polymers may be useful and one route generally useful in the production of conjugated polymers is the Suzuki reaction (Synthetic Communications 11(7) , 513, 1981) . This reaction typically involves the polymerization of an aromatic bis boronic acid or bis boronic ester with a dibromo aromatic monomer in the presence of a palladium-based catalyst and an aqueous base.
  • Such bis boronic esters for use in polymerization reactions are conventionally produced from the corresponding dibromide by the synthetic route shown in Figure 1.
  • the dibromide is first reacted with 2 equivalents of butyl lithium.
  • the resulting diorganometallic compound is then reacted with a trialkylborate such as triisopropoxy borane, B(OiPr) 3 , to produce the bis-dialkylborate intermediate (in this case, the bis-diisopropoxyborane intermediate) , which is then hydrolyzed in situ to produce the bis boronic acid.
  • esterification is carried out.
  • a typical alcohol used in the esterification is 1, 2-dihydroxyethane to produce the 5-membered cyclic ester. This type of synthetic route is disclosed for example in Macromol . Rapid Commun . , 1 1, pp .
  • An aim of the present invention is to provide a more efficient method for producing aromatic monomers having at least two boronic acid groups or two boronic ester groups .
  • Another aim of this invention is to provide a method for purifying aromatic monomers having at least two boronic acid groups with a view to producing boronic ester monomers of higher purity.
  • boronic acid and boronic ester used hereunder refer to monomers having at least two boronic acid groups or at least two boronic ester groups, respectively.
  • step (b) converting the compound provided in step (a) to Z-Ar- Z, wherein each Z is independently a trialkyl silyl radical;
  • step (c) reacting the compound formed in step (b) with BX 3 to form the intermediate [X 2 B-Ar-BX 2 ] , wherein each X is independently a halogen radical;
  • step (d) hydrolysing the intermediate obtained in step (c) so as to form the boronic acid.
  • M is preferably an alkali metal radical such as Li.
  • Step (b) is preferably carried out using a trialkyl silyl halide, preferably trimethyl silyl chloride.
  • Step (c) is preferably carried out using BBr 3 .
  • step (iii) treating the salt isolated in step (ii) with an acid so as to form a solution of a purified boronic acid.
  • steps (i) , (ii) and (iii) are repeated at least once again.
  • Step (i) is preferably carried out using an alkaline aqueous solution such as an aqueous solution of an inorganic hydroxide such as alkali metal hydroxides, alkaline earth metal hydroxides, or ammonium hydroxide, or an aqueous solution of a carbonate.
  • an alkaline aqueous solution such as an aqueous solution of an inorganic hydroxide such as alkali metal hydroxides, alkaline earth metal hydroxides, or ammonium hydroxide, or an aqueous solution of a carbonate.
  • Sodium hydroxide and potassium hydroxide are particularly preferred. According to a preferred embodiment, it is carried out in the presence of an organic solvent in which the boronic acid is soluble.
  • Step (ii) is preferably carried out by filtration.
  • Step (iii) may be carried out using mineral or organic acids . It is preferably carried out using an acidic aqueous solution such as an aqueous solution of hydrochloric acid. According to a preferred embodiment, it is carried out in the presence of an organic solvent in which the boronic acid is soluble.
  • an acidic aqueous solution such as an aqueous solution of hydrochloric acid. According to a preferred embodiment, it is carried out in the presence of an organic solvent in which the boronic acid is soluble.
  • a process of producing an aromatic monomer having at least two boronic ester groups comprising the steps of: preparing a boronic acid in accordance with the process according to the first aspect of the present invention; and esterifying the purified boronic acid.
  • the process according to the third aspect of the present invention preferably further comprises a step of purifying the boronic acid by the process according to the second aspect of the present invention prior to esterification.
  • the boronic ester preferably has the general formula, (R 1 ⁇ ) 2 B-Ar-B (OR 1 ) 2 or is a cyclic boronic ester having the general formula, (OR 2 0) B-Ar-B (OR 2 0) , wherein Ar is a divalent aromatic radical; R 1 is preferably a Ci to C 6 alkyl radical; and R 2 is preferably a non-substituted or substituted ethenyl or propenyl radical, or a substituted or non-substituted divalent aromatic radical.
  • the esterification step is preferably carried out using a divalent alcohol selected from the group consisting of 1, 2-dihydroxybenzene, 1, 2-dihydroxyethane, 1 / 3- dihydroxypropane and 2, 3-dimethyl-2, 3-dihydroxy butane.
  • a divalent alcohol selected from the group consisting of 1, 2-dihydroxybenzene, 1, 2-dihydroxyethane, 1 / 3- dihydroxypropane and 2, 3-dimethyl-2, 3-dihydroxy butane.
  • the overall yields achieved with the process for producing aromatic boronic ester monomers of 100% purity (as measured by reverse phase HPLC) according to the present invention are 50 to 60%, which is significantly higher than the synthetic routes conventionally known and used for the preparation of bis boronic esters. This is particularly surprising for the following reason.
  • a process of producing a conjugated polymer comprising polymerizing a first aromatic monomer together with a second aromatic monomer having at least two reactive halide functional groups, the first aromatic monomer being one selected from the group consisting of an aromatic monomer having at least two boronic acid groups produced by the process according to the first aspect of the present invention and an aromatic monomer having at least two boronic ester groups produced by the process according to the third aspect of the present invention.
  • Ar preferably comprises a substituted or non-substituted phenylene, bisphenylene or a fluorene radical.
  • conjugated polymer includes both fully conjugated polymers (i.e. polymers which are conjugated along the entire length of the polymer chain) and partially conjugated polymers (i.e. polymers whose chain includes both conjugated segments and non-conjugated segments .
  • a process for the production of an optical device or a component for an optical device which comprises providing a substrate and producing a polymer by the process according to the fourth aspect of the present invention, wherein the polymer is supported by the substrate.
  • the optical device may be an electroluminescent device.
  • Figure 1 shows a conventional synthetic route for producing bis boronic esters
  • Figure 2 shows a synthetic route for producing bis boronic esters according to an embodiment of the present invention .
  • Figure 3 shows a schematic representation of an optical device according to the invention.
  • Figure 2 illustrates a synthetic route for producing 9, 9' -dioctylfluorene-2, 7-di (ethylenylboronate) according to an embodiment of the present invention.
  • Butyllithium 160 ml of 2.5 M solution in hexane, 0.4 mol, 1.1 equivalents per bromide was added fairly quickly whilst maintaining the temperature below ⁇ -50 °C .
  • the bromide had all dissolved and at around three quarters addition 2, 7-dilithio-9, 9- dioctylfluorene started to precipitate.
  • the slurry of the dilithiofluorene was stirred for a further half an hour.
  • T SC1 Fresh trimethylsilyl chloride (T SC1) (60 ml, 0.475 mol) was added quickly while maintaining the temperature below -30 °C . The cooling bath was removed and the solution allowed to warm to room temperature. TLC analysis (hexane eluent) showed a single spot close to the solvent front. The solution was transferred to a single-neck flask and the solvents were removed by rotary evaporation. Hexane (300 ml) was added to the residue and the resulting solution was filtered to remove the LiCl, washing thoroughly with more hexane. The hexane was removed and the remaining liquor was subject to high vacuum to remove all traces of THF and hexane. The yield of 2 , 7-di (trimethylsilyl) -9, 9-dioctylfluorene was quantitative i.e. close to 100%.
  • the di-TMS (trimethylsilyl) derivative was transferred to a fresh 2 L three-neck flask (equipped with nitrogen inlet, rubber septum and thermometer) with 150 ml dry dichloromethane and the solution was cooled under nitrogen to ⁇ -78 °C during which time it crystallised.
  • Boron tribromide 60 ml, -1.5 equivalents per TMS group was added over five minutes .
  • the appearance of a green colour (which varies in intensity) accompanied the addition of the first one or two millilitres.
  • the mixture was allowed to warm to room temperature and was stirred for a further two hours. (Cooling of the solution at this point to ⁇ -10 °C resulted in crystallisation of the 2,7- bis (dibromoborane) -9, 9-dioctylfluorene) .
  • the room temperature solution was then poured into 2L of water contained in a 5L beaker upon which there was much evolution of HBr gas.
  • the bis boronic acid began to solidify and the dark green colour disappeared.
  • the solid was then transferred to a large mortar and ground to a powder under water.
  • the powdered diacid was filtered and washed copiously with water and suction dried to remove most of the water.
  • the solid was then added gradually to a rapidly stirred mixture of 5 M HCl (600 ml) and ether (600 ml) contained in a 21 conical flask. After about half an hour the regenerated diacid was contained in the ether layer, which was separated and washed with 3 x 800 ml and then dried and treated with a little charcoal and filtered into a IL flask. The ether was removed and a little acetonitrile added to cause precipitation.
  • the acetonitrile was removed and 800 ml of toluene and ethylene glycol (20 g) were added. The mixture was heated overnight and the water produced removed on a Dean-Stark trap (8.5 ml collected). The toluene was removed and the resulting oil dissolved in boiling acetonitrile (600 ml) and left to cool to room temperature. Cooling was continued in the fridge. The crystals were filtered and washed with plenty of acetonitrile and dried.
  • the diester was then further recrystallised from 300 ml hexane to yield 50g of product (100% purity) .
  • Conjugated polymers can be produced from these diesters using the Suzuki reaction, wherein the diester is polymerized with an aromatic monomer having two reactive halide functional groups in the presence of a palladium catalyst such as tetrakisphenylphosphinepalladium.
  • a palladium catalyst such as tetrakisphenylphosphinepalladium.
  • Figure 3 shows in a purely schematic way the order of layers in an electroluminescent device generally designated 1.
  • substrate 2 which is typically a transparent substrate such as glass
  • anode 3 which may be a layer of transparent indium tin oxide.
  • hole transporting layer 3 which may be a polyethylene dioxythiophene, on which is disposed emissive layer 4, which may be a polymer produced from boronic esters prepared according to the process of the present invention.
  • Layer 5 is an electron transport layer such as poly (styrenesulphonic acid) doped polyethylenedioxythiophene .
  • Layer 6 is a cathode which may be a lithium aluminium layer.

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Abstract

A process of preparing a boronic acid having the general formula, (OH)2B-Ar-B(OH)2, wherein Ar is a substituted or non-substituted divalent aromatic radical, the process comprising the steps of: (a) providing an organometallic compound, M-Ar-M, wherein each M is independently a monovalent metal radical; (b) converting the compound provided in step (a) to Z-Ar-Z, wherein each Z is independently a trialkyl silyl radical; (c) reacting the compound formed in step (b) with BX3 to form the intermediate [X2B-Ar-BX2], wherein each X is independently a halogen radical; and (d) hydrolysing the intermediate obtained in step (c) so as to form the boronic acid.

Description

PREPARATION OF BENZENEDIBORONIC ACID VIA A DISILYLATED ARYL-INTERMEDIATE
The present invention relates to a process for synthesizing monomers for preparing polymers such as a conjugated polymer for use in an optical device such as an electroluminescent device.
Organic electroluminescent devices are known which employ an organic material for light emission. For example, O90/13148 describes such a device comprising a semiconductor layer comprising a polymer film which comprises at least one conjugated polymer situated between electrodes. The polymer film in this case comprises a poly (para-phenylene vinylene) (PPV) film which is capable of light emission when electrons and holes are injected therein. Other polymer layers capable of transporting holes or transporting electrons to the emissive layer may be incorporated into such devices. The bandgap of PPV and other poly(arylene vinylene) polymers may be tuned to modulate the wavelength, quantum efficiency and/or refractive index thereof, as described in EP-A-0544795.
Preparation of poly(arylene vinylene) s for use in optical devices has been conveniently carried out by a precursor route where thermal elimination of leaving groups gives rise to a conjugated polymer, or by other routes such as a dehydrohalogenation reaction. However, poly(arylene vinylene) s are not the only class of polymers which are suitable for use in optical devices. Other aryl- containing polymers may be useful and one route generally useful in the production of conjugated polymers is the Suzuki reaction (Synthetic Communications 11(7) , 513, 1981) . This reaction typically involves the polymerization of an aromatic bis boronic acid or bis boronic ester with a dibromo aromatic monomer in the presence of a palladium-based catalyst and an aqueous base. Since aromatic bis boronic acids tend to be very hydrophilic picking up moisture on storage and are difficult to purify, it is common to use the corresponding bis boronic ester. Under the polymerisation reaction conditions employed, the boronic ester is hydrolysed by the aqueous base to form the corresponding boronic acid as an intermediate, which in turn forms a hydroxylated boronate salt through reaction with the aqueous base. It is this hydroxylated boronate salt which is the reactive monomer species in the polymerisation reaction.
Such bis boronic esters for use in polymerization reactions are conventionally produced from the corresponding dibromide by the synthetic route shown in Figure 1.
With reference to Figure 1, the dibromide is first reacted with 2 equivalents of butyl lithium. The resulting diorganometallic compound is then reacted with a trialkylborate such as triisopropoxy borane, B(OiPr)3, to produce the bis-dialkylborate intermediate (in this case, the bis-diisopropoxyborane intermediate) , which is then hydrolyzed in situ to produce the bis boronic acid. Finally, esterification is carried out. A typical alcohol used in the esterification is 1, 2-dihydroxyethane to produce the 5-membered cyclic ester. This type of synthetic route is disclosed for example in Macromol . Rapid Commun . , 1 1, pp . 239-252 (1996) . However, this synthetic route has the drawback that the overall yield is somewhat low, typically about 20-35%, which is surprising given the excellent yields achieved with this route in the preparation of the mono boronic ester equivalent. This reduction in yield on going from the mono boronic acid or ester to the bis boronic ester was considered to be a problem with all conventional synthetic routes for the preparation of aromatic boronic esters .
Other synthetic routes are known for the preparation of monoboronic esters such as the synthetic route disclosed in J. Am . Chem . Soc . 1992 , 11 4 , 1018-1 025 . However, only relatively poor overall yields have been achieved with this route compared to the route disclosed in Macromol . Rapid Commun . , 1 1, pp . 239-252 (1996) in the preparation of monoboronic esters. It has therefore been widely expected that this route would give poorer overall yields than the route disclosed in Macromol . Rapid Commun . , 1 1 , pp . 239-252 (1996) in respect of the preparation of bisboronic esters.
An aim of the present invention is to provide a more efficient method for producing aromatic monomers having at least two boronic acid groups or two boronic ester groups .
Another aim of this invention is to provide a method for purifying aromatic monomers having at least two boronic acid groups with a view to producing boronic ester monomers of higher purity.
Unless stated otherwise, the terms boronic acid and boronic ester used hereunder refer to monomers having at least two boronic acid groups or at least two boronic ester groups, respectively.
According to one aspect of the present invention, there is provided a process of preparing a boronic acid having the general formula, (OH) 2B-Ar-B (OH) 2, wherein Ar is a substituted or non-substituted divalent aromatic radical, the process comprising the steps of:
(a) providing an organometallic compound, M-Ar-M, wherein each M is independently a monovalent metal radical;
(b) converting the compound provided in step (a) to Z-Ar- Z, wherein each Z is independently a trialkyl silyl radical;
(c) reacting the compound formed in step (b) with BX3 to form the intermediate [X2B-Ar-BX2] , wherein each X is independently a halogen radical; and
(d) hydrolysing the intermediate obtained in step (c) so as to form the boronic acid.
M is preferably an alkali metal radical such as Li.
Step (b) is preferably carried out using a trialkyl silyl halide, preferably trimethyl silyl chloride.
Step (c) is preferably carried out using BBr3.
According to a second aspect of the present invention, there is provided a process of purifying a boronic acid having the general formula, (OH) 2B-Ar-B (OH) 2, wherein Ar is a substituted or non-substituted divalent aromatic radical, the process comprising the steps of: (i) treating a solution of the boronic acid with a base to precipitate the salt, [ (OH) 3B-Ar-B (OH) 3] 2".2M+, wherein each M+ is independently a monovalent cation; (ii) isolating the salt obtained in step (i) ;
(iii) treating the salt isolated in step (ii) with an acid so as to form a solution of a purified boronic acid.
In a preferred embodiment, steps (i) , (ii) and (iii) are repeated at least once again.
Step (i) is preferably carried out using an alkaline aqueous solution such as an aqueous solution of an inorganic hydroxide such as alkali metal hydroxides, alkaline earth metal hydroxides, or ammonium hydroxide, or an aqueous solution of a carbonate. Sodium hydroxide and potassium hydroxide are particularly preferred. According to a preferred embodiment, it is carried out in the presence of an organic solvent in which the boronic acid is soluble.
Step (ii) is preferably carried out by filtration.
Step (iii) may be carried out using mineral or organic acids . It is preferably carried out using an acidic aqueous solution such as an aqueous solution of hydrochloric acid. According to a preferred embodiment, it is carried out in the presence of an organic solvent in which the boronic acid is soluble.
According to a third aspect of the present invention, there is provided a process of producing an aromatic monomer having at least two boronic ester groups, the process comprising the steps of: preparing a boronic acid in accordance with the process according to the first aspect of the present invention; and esterifying the purified boronic acid. The process according to the third aspect of the present invention preferably further comprises a step of purifying the boronic acid by the process according to the second aspect of the present invention prior to esterification.
The boronic ester preferably has the general formula, (R1©) 2B-Ar-B (OR1) 2 or is a cyclic boronic ester having the general formula, (OR20) B-Ar-B (OR20) , wherein Ar is a divalent aromatic radical; R1 is preferably a Ci to C6 alkyl radical; and R2 is preferably a non-substituted or substituted ethenyl or propenyl radical, or a substituted or non-substituted divalent aromatic radical.
The esterification step is preferably carried out using a divalent alcohol selected from the group consisting of 1, 2-dihydroxybenzene, 1, 2-dihydroxyethane, 1/3- dihydroxypropane and 2, 3-dimethyl-2, 3-dihydroxy butane.
The overall yields achieved with the process for producing aromatic boronic ester monomers of 100% purity (as measured by reverse phase HPLC) according to the present invention are 50 to 60%, which is significantly higher than the synthetic routes conventionally known and used for the preparation of bis boronic esters. This is particularly surprising for the following reason.
As mentioned earlier, the use of this reaction for the preparation of mono boronic esters is known in the prior art (see J. Am . Chem . Soc . 1992 , 11 4 , 1 01 8-1 025) but the reproducible yields obtained are lower than the reproducible yields which have been reported for the kind of reaction described in Ma cromol . Rapid Commun . , 1 1, pp . 239-252 (1996) in the preparation of mono boronic esters (for which yields of greater than 90% have been reported) . It was therefore expected given the above- mentioned general trend of a reduction in yield going from the preparation of the mono boronic ester to the polyboronic ester, that the application of this reaction to the preparation of polyboronic esters would only give poorer yields than those obtained with the reaction disclosed in Macromol . Rapid Commun . , 1 1, pp . 239-252 (1996) . Contrary to this expectation, the inventors of the present invention have found that the yield is in fact significantly higher than that obtained with the reaction disclosed in Ma cromol . Rapid Commun . , 1 7, pp . 239-252 (1996) .
According to a fourth aspect of the present invention, there is provided a process of producing a conjugated polymer comprising polymerizing a first aromatic monomer together with a second aromatic monomer having at least two reactive halide functional groups, the first aromatic monomer being one selected from the group consisting of an aromatic monomer having at least two boronic acid groups produced by the process according to the first aspect of the present invention and an aromatic monomer having at least two boronic ester groups produced by the process according to the third aspect of the present invention.
Ar preferably comprises a substituted or non-substituted phenylene, bisphenylene or a fluorene radical.
The term conjugated polymer includes both fully conjugated polymers (i.e. polymers which are conjugated along the entire length of the polymer chain) and partially conjugated polymers (i.e. polymers whose chain includes both conjugated segments and non-conjugated segments .
According to a fifth aspect of the present invention, there is provided a process for the production of an optical device or a component for an optical device, which comprises providing a substrate and producing a polymer by the process according to the fourth aspect of the present invention, wherein the polymer is supported by the substrate.
The optical device may be an electroluminescent device.
An embodiment of the present invention shall be described hereunder, by way of example only, with reference to the accompanying drawings in which :-
Figure 1 shows a conventional synthetic route for producing bis boronic esters;
Figure 2 shows a synthetic route for producing bis boronic esters according to an embodiment of the present invention .
Figure 3 shows a schematic representation of an optical device according to the invention.
Figure 2 illustrates a synthetic route for producing 9, 9' -dioctylfluorene-2, 7-di (ethylenylboronate) according to an embodiment of the present invention.
A detailed description of a method of preparing 9,9- dioctylfluorene-2, 7-di (ethylenyl boronate) according to an embodiment of the present invention will be described hereunder by way of example only. A 2L three-neck flask equipped with a magnetic stirrer, a nitrogen inlet, a rubber septum and a low temperature thermometer was charged with a solution of 2,7-dibromo- 9, 9' -dioctylfluorene (100 g, 0.182 mol) in 500 ml of dry THF. With the aid of a dry ice/acetone bath the solution was cooled to ~ -78 °C during which time the dibromide precipitated. Butyllithium (160 ml of 2.5 M solution in hexane, 0.4 mol, 1.1 equivalents per bromide) was added fairly quickly whilst maintaining the temperature below ~ -50 °C . At half addition the bromide had all dissolved and at around three quarters addition 2, 7-dilithio-9, 9- dioctylfluorene started to precipitate. After complete addition the slurry of the dilithiofluorene was stirred for a further half an hour.
Fresh trimethylsilyl chloride (T SC1) (60 ml, 0.475 mol) was added quickly while maintaining the temperature below -30 °C . The cooling bath was removed and the solution allowed to warm to room temperature. TLC analysis (hexane eluent) showed a single spot close to the solvent front. The solution was transferred to a single-neck flask and the solvents were removed by rotary evaporation. Hexane (300 ml) was added to the residue and the resulting solution was filtered to remove the LiCl, washing thoroughly with more hexane. The hexane was removed and the remaining liquor was subject to high vacuum to remove all traces of THF and hexane. The yield of 2 , 7-di (trimethylsilyl) -9, 9-dioctylfluorene was quantitative i.e. close to 100%.
The di-TMS (trimethylsilyl) derivative was transferred to a fresh 2 L three-neck flask (equipped with nitrogen inlet, rubber septum and thermometer) with 150 ml dry dichloromethane and the solution was cooled under nitrogen to ~ -78 °C during which time it crystallised. Boron tribromide (60 ml, -1.5 equivalents per TMS group) was added over five minutes . The appearance of a green colour (which varies in intensity) accompanied the addition of the first one or two millilitres. After complete addition the mixture was allowed to warm to room temperature and was stirred for a further two hours. (Cooling of the solution at this point to ~ -10 °C resulted in crystallisation of the 2,7- bis (dibromoborane) -9, 9-dioctylfluorene) .
The room temperature solution was then poured into 2L of water contained in a 5L beaker upon which there was much evolution of HBr gas. The bis boronic acid began to solidify and the dark green colour disappeared. The solid was then transferred to a large mortar and ground to a powder under water. The powdered diacid was filtered and washed copiously with water and suction dried to remove most of the water.
Meanwhile a solution of KOH (300 g) in water (800 ml) was prepared in a 31 beaker and cooled to room temperature. The diacid was dissolved in 200 ml ether and the yellow solution was poured with rapid stirring into the KOH solution. A thick white precipitate of the dipotassium boronate salt was produced. Stirring was continued for ten minutes to ensure that all the acid had reacted. The two phase mixture was filtered in a large glass sinter funnel, sucked to partial dryness and then washed with plenty of water and then ether. The solid was transferred to another 3L beaker and thoroughly stirred with a further 2L ether and then filtered again. The solid was then added gradually to a rapidly stirred mixture of 5 M HCl (600 ml) and ether (600 ml) contained in a 21 conical flask. After about half an hour the regenerated diacid was contained in the ether layer, which was separated and washed with 3 x 800 ml and then dried and treated with a little charcoal and filtered into a IL flask. The ether was removed and a little acetonitrile added to cause precipitation.
The acetonitrile was removed and 800 ml of toluene and ethylene glycol (20 g) were added. The mixture was heated overnight and the water produced removed on a Dean-Stark trap (8.5 ml collected). The toluene was removed and the resulting oil dissolved in boiling acetonitrile (600 ml) and left to cool to room temperature. Cooling was continued in the fridge. The crystals were filtered and washed with plenty of acetonitrile and dried.
61.5 g of the product were obtained representing a yield of 63.5%. The purity of the product was measured to be 94% using HLPC.
The diester was then further recrystallised from 300 ml hexane to yield 50g of product (100% purity) .
Conjugated polymers can be produced from these diesters using the Suzuki reaction, wherein the diester is polymerized with an aromatic monomer having two reactive halide functional groups in the presence of a palladium catalyst such as tetrakisphenylphosphinepalladium.
Figure 3 shows in a purely schematic way the order of layers in an electroluminescent device generally designated 1. Disposed on substrate 2, which is typically a transparent substrate such as glass, is anode 3 which may be a layer of transparent indium tin oxide. Adjacent layer 2 is hole transporting layer 3, which may be a polyethylene dioxythiophene, on which is disposed emissive layer 4, which may be a polymer produced from boronic esters prepared according to the process of the present invention. Layer 5 is an electron transport layer such as poly (styrenesulphonic acid) doped polyethylenedioxythiophene .. Layer 6 is a cathode which may be a lithium aluminium layer.

Claims

1. A process of preparing a boronic acid having the general formula, (OH) 2B-Ar-B (OH) 2, wherein Ar is a substituted or non-substituted divalent aromatic radical, the process comprising the steps of:
(a) providing an organometallic compound, M-Ar-M, wherein each M is independently a monovalent metal radical;
(b) converting the compound provided in step (a) to Z-Ar- Z, wherein each Z is independently a trialkyl silyl radical;
(c) reacting the compound formed in step (b) with BX3 to form the intermediate [X2B-Ar-BX ] , wherein each X is independently a halogen radical; and
(d) hydrolysing the intermediate obtained in step (c) so as to form the boronic acid.
2. A process according to claim 1 wherein M is an alkali metal radical.
3. A process according to claim 2 wherein M is Li.
4. A process according to any preceding claim wherein step (b) is carried out using a trialkyl silyl halide.
5. A process according to claim 4 wherein step (b) is carried out using a trialkyl silyl chloride.
6. A process according to any preceding claim wherein Z is a trimethylsilyl radical.
7. A process according to any preceding claim wherein X is Br .
8. A process of purifying a boronic acid having the general formula, (OH) 2B-Ar-B (OH) 2, wherein Ar is a substituted or non-substituted divalent aromatic radical, the process comprising the steps of:
(i) treating a solution of the boronic acid with a base to precipitate the salt, [ (OH) 3B-Ar-B (OH) 3] 2".2M+, wherein each M+ is independently a monovalent cation;
(ii) isolating the salt obtained in step (i); and
(iii) treating the salt isolated in step (ii) with an acid so as to form a solution of a purified boronic acid.
9. A process according to claim 8 wherein M is sodium.
10. A process according to claim 8 wherein the base comprises an alkaline aqueous solution.
11. A process according to claim 10 wherein the base comprises an aqueous solution of sodium hydroxide.
12. A process according to any one of claims 8 to 11 wherein the acid comprises an acidic aqueous solution.
13. A process according to claim 12 wherein the acid comprises an aqueous solution of hydrochloric acid.
14. A process according to any one of claims 8 to 13 wherein step (ii) is carried out by filtration.
15. A process according to any of claims 8 to 14 wherein step (i) is carried out in the presence of an organic solvent in which the boronic acid is soluble.
16. A process according to any of claims 8 to 15 wherein step (iii) is carried out in the presence of an organic solvent in which the boronic acid is soluble.
17. A process of producing an aromatic monomer having at least two boronic ester groups, the process comprising the steps of: preparing a boronic acid in accordance with any one of claims 1 to 7; and esterifying the boronic acid.
18. A process according to claim 17 further comprising the step of purifying the boronic acid by the process according to any one of claims 8 to 16 before esterifying the boronic acid.
19. A process according to claim 17 or claim 18 wherein the aromatic boronic ester monomer has the general formula, { ^O) 2B-Ar-B (OR1) 2 or (OR20) B-Ar-B (OR20) , wherein Ar is a divalent aromatic radical, R1 is a Ci to C6 alkyl radical, and R2 is a non-substituted or substituted ethenyl or propenyl radical, or a substituted or non- substituted divalent aromatic radical.
20. A process according to any one of claims 17 to 19 wherein the esterification step is carried out using a divalent alcohol selected from the group consisting of 1, 2-dihydroxybenzene, 1, 2-dihydroxyethane, 1,3- dihydroxypropane and 2, 3-dimethyl-2, 3-dihydroxy butane.
21. A process of producing a conjugated polymer comprising polymerising a first aromatic monomer together with a second aromatic monomer having at least two reactive halide functional groups, the first aromatic monomer selected from the group consisting of an aromatic monomer having at least two boronic acid groups produced by the process according to any of claims 1 to 7, and an aromatic monomer having at least two boronic ester groups produced according to the process defined in any one of claims 17 to 20.
22. A process according to any preceding claim wherein Ar comprises a phenylene, bisphenylene or a fluorene radical which are substituted or non-substituted.
23. A process for the production of an optical device or a component for an optical device, which comprises providing a substrate and producing a polymer in accordance with the process of claim 21, wherein the polymer is supported by the substrate.
24. A process according to claim 23 wherein the optical device comprises an electroluminescent device.
PCT/GB2000/003554 1999-09-16 2000-09-15 Preparation of benzenediboronic acid via a disilylated aryl-intermediate WO2001019834A1 (en)

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